Method for converting hydrocarbon oils



July 21, 1942- w. J. DEGNEN E-rAL 2,290,580

METHOD FIOR CONVERTING HYDROARBON OILS part of the instant specification,

Patented July 4.21, 1942 UNITED STATE William J. Degnen,

Jersey City, and Pei-civ N. J., assigno'rs to -13 Claims.

to a method for convertoils, and more particularly to a Our invention relates ing hydrocarbon method for converting high boiling hydrocarbons in the presence of 1a, suitable catalyst in order to convert the hydrocarbon oil into the desired products. For various reasons, the catalyst becomes less effective with use and it is necessary to revivify it. During an operation, the catalyst varies in eiectiveness from maximum to minimum so that, for any given catalyst bed, only average effectiveness is obtained.

Cracking is an endothermic reaction, and oil heated to cracking temperature and passed into a cracking zone will, as the reaction progresses, cool, and with cooling there crease in the cracking reaction until no cracking occurs. In our above mentioned co-pending application, Serial No. 199,702, we have provided means for supplying heat to the reaction chamber during the cracking reaction in order to increase the 'amount of cracking per pass. In the instant application, We propose to divide the catalytic bed or reaction chamber into a plurality of stages so that the partially cracked material may be heated between stages.

One object of our invention is to provide a method of cracking in' the presence of a catalyst, in which the catalyst material is continuously be ing removed and revivied, in a plurality of beds with'an intermediate step of heating.

Another object of our invention is to provide a method of cra-cking Yin the presence of a catalyst in which the catalytic bed is continuously being removed and reviviiied so that the catalytic bed will remain of substantially constant effectiveness. f

is a progressive des PAT 2,290,580 l METHOD FOR CONVERTING HYDROCARBON." 'y I oms Cranford. Henry M. Nelly, .lial C. Keith, Jr`., Peapack,

The M. W. Kelloggllompany,` New York, N. Y., a corporation of- Delaware i Application April z, 1938,seriai N. 199,103' 'f (ci. isc-49) 's an improvement of our co- `heated oil or its vapors through a cracking zone Other and further objects.V of our invention will i appear from the following description.

In the accompanying drawing, which forms Y and which is to be read in conjunction therewith, the figure is a schematic view of apparatus capable of carrying out the-process of our invention. In general, our invention contemplates a process in which oil vapors to be converted are brought into contactv witha eattnyst. in a mst conversion zone in*l which the'catalyst is co'ntiriiig :fr .f L ously being replaced so thatthe compos ition'of'` the catalyst chamberwillbe-i andmayjilowto 'heating' 1' equipment without .precautionsbeing taken forfv the oil vapor leaving substantially constant change in its composition., andthe'nto' a second reaction chamber in which vthe catalyst islikef wise continuously being maintained ata constant so that thecracking vaporsv may l f'- i flow to after equipment without. constantly' l watching for changes inits composition','and' thev necessity of varying theopcration ofY theaf'te'rv state of activity,

equipment. This is a major advantage over the intermittent processes of the prior art in which.

the products leaving the catalyst chamber may vary in composition. In an intermittent process, for example, in which hydrocarbon oils are cracked to form gasoline-likehydrocarbons, atv

the beginning of a periodthe vapors leaving the reaction chamber may contain'from 40% to 50% of gasoline, while,.at the end of the period, they may contain as low as 15% to 20% of gasoline.

In the intermittent processes in order vto obtain high cracking per pass, the cracking period must necessarily be short due to the fact .that the catalyst activity falls oi rapidly. In 'a continu'- ous process, the cracking per pass may be raised by increasing the circulation rate of the catalyst per unit of oil charged.

In the intermittent processes, be converted pass through the reaction chamber in contact with catalyst of highest activity only during one part of a period. After this period has vbeen passed the catalyst is progressively decreasing in activity. In our method of continuously circulating a catalyst in contact with the oil vapors, the average lcomposition of the catthe loil vapors to alyst remains substantially constantl and. a portion of the oil vapors always contacts some catalyst of highest activity.

The catalyst being continuously removed from the reaction chamber is continuously revivied and recirculated to the catalyst chamber.

j By splitting the reaction into two stages and supplyingheat to the material during each of the stages, the drop in tem-peraturefwith resultant decrease in cracking is minimized'.

More particularly, referring now to the drawing, the oil to be cracked, which may' be of anyv suitable character, such' as gas oil or the like, is 'pumpedi` through pipe I3 byl pump l2, through convection heating coil l5 in furnace I4, through radiantly heated tubes I6, the oil' being withdrawn from the furnace through transfer pipe A control reflux may be introduced into the separator I8 through pipe I9. Superheated steam -may be delivered into separator I8 through pipe 20 to assist in the separation of the vapors from the heated oil. The unvaporized oil is withdrawn from the separator I8 through pipe 2| and pumped by pump 22 to heat exchanger 23, which is supplied with a cooling medium through by valve 21, to stor- A portion of the unvaporized oil may be recycled for tower valve 32. The hightreatment, sation, for recovery of the converted hydrocarbons.

In the reaction chambers 39 and 39', the heated vapors react to form lighter hydrocarbons in the presence of a catalyst.

.pers II and IIU' is controlled by respective cone type valves I|4 yand I 4', each provided with hydraulic operating means and |I5'. The catalyst material passes from respective feeding ducts IIS and IIS' a rotary rbucket type valve I operated -by an electric motor ||9, through suitable gears The used catalytic material is withdrawn from the reaction chamber 39 by rotary bucket type valve |2| operated by an electric motor I 22. In the same manner, used catalytic material leaves the reaction chamber 39 through a rotary -buck- |23', the exhaust et type valve I2I' operated by an electric motor I2 The motors ||9, |I9, |22 and |22' may be synchronized so that the rate of feeding the rate of withdrawal are kept the same. used catalytic material leaving reaction cham- I, passes into a sealing hopper |23, the exhaust of which is controlled by a cone type valve |24, operated lby a hydraulic operating mechanism I 25. In the same manner, catalytic material leaving the reaction chamber 39' via valve |2I' passes into a sealing hopper of which is controlled by a cone type valve |24' operated by a hydraulic operating mechanism |25'.

The hydraulic operating mechanisms II5, ||5', |25 and |25', are supplied with hydraulic uid through pipes |26, |26', tively. A fluid 4pump |28 catalytic material into y hoppers ||'I and Ill', and to withdraw used catalytic material 'fro' the sealing hoppers |23 and |23'.

An inert gas, such as ue gas, carbon dioxide, or light hydrocarbon gases under suitable pressure the feeding hopper 0'. The pressure of the gas is such that it is slightly in excess of the pressure existing in the catalyst chambers 39 and 39'. The placing of the feeding hoppers IIO and |I0' and the communicating sealing hoppers I I1 and |I| under this pressure will effectively prevent leakage outwardly of cracked vapors. Such leakage as will occur past cone type valves III and |I4' will be of the sealing gas into the sealing hoppers I I'I The capacity of the sealing hoppers is sufficiently greater than |35 and |35 that there will always be a quantity of material present in the sealing hoppers I| 'I and I|I', thus assuring continuity of feed to the ing hopper |I0 and the between sealing hopper reaction chamber 39, and IIII' and reaction chamtrolling valve |31 the pressure Within the hopper |23 is controlled to be slightly in excess of that which exists in pipe 38, and in the reaction chamber 39, so that gas introduced into the sealing hopper |23 will denude or strip the catalytic mal pass through pipe 38 into the reaction chamber Valong with the hot vapors to be reacted.

Correspondingly, sealing gas from manifold |32 passes through pipe 66 through pipe |36', controlled by valve I 31' into discharge-sealing hopper catalytic material.

catalytic material is 23'. By control of valve |31, the pressure withn hopper |23' is controlled to be slightly in exss of that which exists in pipe 60 and in the reaction chamber 39' so that gas introduced into ;he sealing hopper |23 will strip the catalytic ma- :erial of vapors absorbed or mixed therewith. I'he stripped vapors and sealing gas will leave the sealing hopper |23 through apipe 40' controlled by valve 4| and pass through pipe 60 into reaction chamber along with the hot vapors to be reacted.

The catalytic reaction chambers 39 and 39 may be operated with the catalyst feed in parallel or in series. When the operation is in parallel, both valves 64 and 85 are opened so that catalytic material from the catalyst distributing-bin 6| will ow through conduits 62 and 83 into catalyst feeding hoppers H and H0. The motor ||2' operating the conveyor I I in the conveying tube |08' is stopped. The valve 10 controlling the duct 1| leading to the conveyor tube I is closed. The valve 12 controlling the conduit 13 leading to the hopper 14 is opened. Catalytic material discharged intol the catalytic material discharge hopper |35 passes through the duct |31 into the conveyor tube 15 for feeding by conveyor screw 18, which is operated by motor 11, into the hopper 14. Catalytic material from hopper 14 is fed through conveyor tube |38 by conveyor |43 to a catalyst revivifying feeding hopper 205 through a duct 204. The catalytic material discharged from catalytic material discharge hopper |35' passes through duct 13 into hopper 14 with the usedvcatalyticv material being discharged thereinto by conveyor screw 16.

y When the reaction chambers 39 and 39' are operated with the catalyst feed in series, valve 64 is closed while valve 65 is left open. Valve 12 controlling duct 13 is trolling duct 1I is opened. The motor H2' controlling conveyor for operation in conveyor tube |08' is started. Fresh catalytic material from the catalytic material distributing bin 6| is fed to feeding hopper ||0' as before. The discharged catalytic material from catalytic discharge hopper |35' is conveyed by conveyor to the catalyst feedinghopper ||0. The used catalytic material is discharged from the catalytic material discharge hopper |35 through duct |31, for passage into the conveyor tube 15, as before. It will be seen that in the series operation the flow of vapors is countercurrent to the flow of for each chamber in the parallel operation but the counteriiow is half the length of that which obtains in the series operation. In both operations there is a withdrawal of the vapors from the rst reaction chamber with reheating before passage into the second reaction chamber.

The pressure of the sealing gas in the discharge hoppers |35 and |35 exists in the conveyor tube 15, the hopper |38 and the duct 204, as well as in the feeding hopper 205 which feeds the used catalytic ma'- terial to the catalytic revivifying chamber 203.

' The feeding hopper 205 is provided with a cone type valve 206 actuated by hydraulic operating mechanism 201. hopper 205 with the sealing hopper 209.v A rotary bucket type valve 2|0 is operated by motor 2|| for passing the catalytic material to be revivied into the revivifying chamber 203. The reviviiied fying chamber 203 by bucket type valve 2 I2 operated by an electric motor 2|3, for passage into closed, while valve 10 con- 14, the conveyor tube- A duct 208 connects the feeding withdrawn from the revivii conveying means to -vivifled sealing hopper 2|4. The reviv-ified catalytic material leaves hopper 2|4 past a cone type valve 2|5. The cone type valve 2I5 is provided with hydraulic operating mechanism 2|6. The hydraulic opfrating mechanisms 201 and 2|6 are supplied with hydraulic operating uid through pipes 2|1 and 2|8 which are in turn supplied through pipe 2|9 by pump |28. It will vbe observed that the six hydraulic operating mechanisms, that is,.mechanis ms H5, H5', |25, |25', 201 and 2|.6 are interconnected so that the revivifying operation and cracking operation are synchronized to continuously supply catalyst and revivify it for reuse. In other words, the catalyst material is continuously passed from the revivifler to the reaction chamber. back to the revivifier in a continuous circulating ring thereby providing for the circulation of the catalyst at an elevated temperature throughout the process, and the hot vapors to be cracked are continuously passed in contact with the moving stream of catalytic material. The revivified catalytic material from sealing chamber 2|4 passes the cone type valve 2| 5 for delivery into discharge hopper 220.

A vibratingscreen 22| provided with vibratory actuating means- 222 screens out the iines which pass into a lines collecting hopper 223. The reyscreened catalytic material passes through duct 224 into a hopper 225 from which it is withdrawn through duct 226 for passage to the feeding conveyor tube |08, for carriage by the catalyst distributing bin 0|. Fresh catalytic material to replace the fines is supplied from hopper 221 through duct 228 controlled by valve 229,'and auxiliary hopper 230 and duct 23|, vwhich is controlled by valve 232. It will be noted that the catalytic revivier The counterflow also holds lterial to pass through duct 23| and -delivered through 233 to an is under pressure, and the auxiliary hopper 230 acts as a lock. In other words, by operating valve 229, catalytic material is fed from-hopper 221 to the auxiliary hopper 230. Valve 229 is then closed and valve 232 is opened, permitting mainto the revivied catalytic material discharge 'hopper 220.

The revivification of the catalytic material in the revivifier chamber 203 is by oxidation of the carbon and adsorbed heavy hydrocarbons. Air is taken from the atmosphere through air intake pipe 232 and is compressed by compressor |8| air receiver tank 234 which supplies air through pipe |49.

In starting the unit, the valve |5| is opened to supply air to the burner |52, to which fuel gas is supplied through pipe |53, the hot gases passing through duct into the revivifying chamber 203. After the chamber is suiiiciently heated,

valve |5| is closed and valve |63 is opened to. permit air to pass through duct |80 into the revivifying chamber.

The gases ofl combustion from the revivication reaction are withdrawn from the revivifying chamber 203 through a duct |64 for passage to a iiue |1| by opening dampers |12 and |13. A blower |19 is adapted to withdraw flue gas through duct |19 for delivery through duct |11 into duct |80 to the revivifying chamber for controlling the temperature of the reviviflcation reaction. Preferably in duct |18 is interposed any type of cooler such as a wasteheat boiler to reduce the gases to the desired temperature.

Flue gas is withdrawn from duct |18 through pipe |82 for compression by compressor |84 and delivery to the sealing nue gas receiver |86. The

' vary from 800 F. to 950 sealing ilue gas receiver IIB supplies sealing gas to manifold |32. g

In operating our process, the reaction temperature maintained within the catalyst bed may F. 'I'he catalytic material employed may be any suitable material as, for example, alumina deposited upon silica gel. 'I'he catalyst may pass through the reaction chambers at a space velocity of from two to ten or more barrels per hour of charge per ton of catalyst material in the bed depending on the desired crack per pass.

It is found that the gasoline yield will be anywhere from ten to twenty per cent or more greater than that which will take place in a run under similar conditions made with a stationary is` understood, of course, vthat conditions may be varied within wide limits depending upon the type of hydrocarbon oil being charged and the end products desired.

As the catalyst material -becomes contaminated, it loses its activity. We have found that it is not necessary to completely renew the contaminating material to reactivate the catalyst. For example, where the total carbon absorbed in one run amounted to 17% by weight of the catalyst, it; was found that a reduction of the carbon by burning lin the revivifying chamber to 7.2% by weight of the catalyst gave a catalytic material which was effectively used and compared favorably with an operation in which fresh catalyst was continuously charged.

It is believed from the foregoing that our method will be clear to those skilled in the art. The operation will beunderstood from the foregoing description. It will be seen that we have accomplished the objects of have provided a method of proceeds.

In the intermittent process it is not uncommon to have a gasoline content inthe vapors leaving the reaction chamber at the beginning of the operation of from 40% to. 50%, and a gasoline content of as low as to 20% at the end of L Athe cycle.`

In a copending application, Serial No. 199,702, there is shown a method of supplying the heat of reaction to individual reaction chambers by circulation of a heating medium around the catalyst passing` through the chambers, and in indirect heat exchange therewith. There is also shown a simple chamber wherein the heat of obvious` that various changes may be made in details'within the scope of our claims without f departing from the spirit of our invention. It

1s, therefore, to be understood limited to the speciiic details shown and described.

Having thus described our invention, what we claim is:

1. A process of converting hydrocarbon oils conversion.

2. In a process of cracking hydrocarbon oils into lower boiling hydrocarbons within the gasoline boiling range in which a hydrocarbon oil is heated to crac g temperature, ashed into catalyst and hydrocarbon vapors undergoing conversion.

3. A method of converting hydrocarbon oil into lower boiling hydrocarbons Within the gasoof continuously counterowing hydrocarbon oil heated to a conversion temperature in a first reaction zone with a compact mass of catalyst, continuously supplying catalyst ,material to said reaction zone, continuously removing partially spent catalytic material from said reaction zone, withdrawing the reacted hydrocarbon oil from the rst reaction zone and reheating it to reaction temperature, continuously counterfiowing the reheated hydrocarbon oil at reactiontemperature in a second reaction zone with,a catalyst material, continuously supplying catalyst material to said second reaction zone, and continuously removing partially spent catalytic material from said second reaction zone each of said reaction zones being ma' tained at the desired average reaction temperature by the sensible heat contained in the introduced catalyst and hydrocarbon vapors undergoing conversion.

5. A method as in claim 3 wherein the catalytic material supplied to said first reaction zone is that withdrawn from said second reaction zone.

6. A method as in claim 3 in which freshly regenerated and hot catalytic material is supplied to both reaction zones.

'1. A-method as in claim 3 wherein the catalytic material withdrawn from said rst reaction zone is continuously reactivated and recycled directly into said second reaction zone.

8. A method as in claim 3 wherein the catalytic material Wthdrawn from said rst and said second reaction zone is continuously revivii'led and returned directly to said reaction zones.

9. A method of converting hydrocarbon oil by an endothermic catalytic reaction, steps of heating a hydrocarbon oil to -a conversion temperature, contacting the heated hydrocarbon oil with a moving bed of catalyst particles in a first reaction zone, withdrawing the hydrocarbon oil from the rst reaction zone and reheating it to conversion temperature, and contacting the reheated oil with a moving bed of catalyst particles in a second reaction zone for asuicient period of time to effect conversion, each of said reaction zones being maintained at the desired average conversion temperature by the sensible heat contained in the introduced catalyst andhydrocarbon vapors undergoing conversion.

10. A method of converting hydrocarbon oil by an endothermic catalytic reaction, including the steps of contacting hydrocarbon oil with a moving bed of catalyst particles in a nrst reaction zone maintained at conversion temperature, withdrawing the hydrocarbon oil from the first reaction zone, reheating and contacting hydrocarbon oil thus withdrawn from the first reaction including the zone with a movingbed of 'catalyst particles in a second reaction zone for a sufcient period of time to eect further conversion thereof, each of said reaction zones being maintained at the desired average conversion temperature by the sensible heat contained in the introduced catalyst and hydrocarbon vapors undergoing conversion.

l1. A method of converting hydrocarbon oil by an endothermic catalytic reaction, including the steps of heating hydrocarbon oil to an elevated temperature, contacting the heated oil with a moving bed of catalyst particles in aflrst reaction zone, withdrawing the hydrocarbon oil from the rst reaction zone and reheating hydrocarbon oil thus withdrawn to an elevated temperature, and contacting the reheated oil with a moving bed of catalyst particles in a lsecond reaction zone for a sufficient period of time to effect conversion thereof, each of said reaction zones being maintained at the desired average conversion temperature by the sensible heat contained in the introduced catalyst and hydrocarbon vapors undergoing conversion.

12. A process as defined in claim 11 wherein the used catalyst continuously' withdrawn from both of said reaction zones is passed to a common regeneration zone and the regenerated catalyst is continuously withdrawn from said regeneration zone and returned directly to said reactionzones, 4a portion thereof being returned directly to the first reaction zone and a second portion directly to the second reaction zone.

13. A method of converting hydrocarbon oil into lower boiling hydrocarbons within the gasoline boiling range including the steps of contacting hydrocarbon oil with a bed of catalyst particles circulated through a rst reaction zone maintained at conversion temperature, withdrawing hydrocarbon oil from the rst-reaction zone and reheating hydrocarbon oil thus withdrawn to an elevated temperature, and contacting the reheated oil with a bed of catalyst particles circulated through a second reaction zone, for a sufcient period of time to effect conversion thereof, each of said reaction zones being maintained at the desired average conversion temperature by the sensible heantained in the introduced catalyst and hydr arbon vapors undergoing conversion, the catalytic material continuously supplied to one of said zones being that continuously withdrawn from the other reaction zone. i

lWILLIAM J. DEGNEN.

HENRY M. NELLY, Ja. PERCIVAL C. KEITH, Ja. 

